CN115843189B - Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains - Google Patents
Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains Download PDFInfo
- Publication number
- CN115843189B CN115843189B CN202211652239.8A CN202211652239A CN115843189B CN 115843189 B CN115843189 B CN 115843189B CN 202211652239 A CN202211652239 A CN 202211652239A CN 115843189 B CN115843189 B CN 115843189B
- Authority
- CN
- China
- Prior art keywords
- perovskite
- film
- coating
- solar cell
- isopropanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a method for improving the performance of a perovskite solar cell through secondary growth of perovskite crystal grains, which comprises the following specific operations: cleaning a transparent conductive substrate, spin-coating a film on the surface of the substrate, continuing spin-coating a perovskite precursor solution on the film, spin-coating a thioglycollic ethyl acetate/isopropanol solution on the surface of the annealed perovskite film, and obtaining PVK crystal grains with larger crystal grain size in a secondary annealing mode, thereby reducing the existence of crystal boundaries with high defect state density and being beneficial to the efficient transmission of carriers; meanwhile, due to the existence of sulfhydryl and carbonyl functional groups in ET molecules, defect states existing on the PVK surface are effectively passivated, the performance of the PVK film is further improved, and finally the performance of the perovskite solar cell device based on ET/IPA treatment is obviously improved.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a method for improving the performance of a perovskite solar cell through secondary growth of perovskite crystal grains.
Background
Solar energy is widely used in the field of photovoltaic power generation as a clean energy source. Solar cells have proven to be effective photoelectric conversion means as a medium for converting solar energy into electrical energy. Perovskite materials have been successfully used in the preparation of solar cells as novel photoelectric conversion materials. For perovskite solar cells, the development bottleneck faced by the current perovskite solar cells mainly comprises that a larger lifting space still exists between the photoelectric conversion efficiency and the theoretical efficiency limit value; meanwhile, due to the ionic property of the perovskite material, a large number of defect points (such as uncoordinated lead ions) exist at the crystal boundary of the surface of the film, and the defect points become main invasion sites of the perovskite eroded by external factors (water and oxygen), so that the stability of the perovskite film is affected.
In view of this, passivation strategies for perovskite surface defects have often been investigated as an effective method for improving perovskite solar cell performance. However, the passivation of the functional small molecules can only modify the defect points existing at the perovskite film grain boundaries, but has the effect of reducing the generation of the perovskite film grain boundaries.
Disclosure of Invention
The invention solves the technical problems that: the defects of the perovskite surface which are passivated by the functional micromolecules are not perfect, namely, only the existing defects at the grain boundaries can be passivated, but the existence of the grain boundaries cannot be reduced. In view of the above technical problems, an object of the present invention is to provide a method for improving the performance of a perovskite solar cell by secondary growth of perovskite crystal grains.
According to the invention, ET molecules are introduced into the surface of the annealed perovskite film, and perovskite crystal grains with larger crystal grain sizes are obtained in a secondary annealing mode, so that the existence of crystal boundaries is effectively reduced, and the quantity of defect points is reduced.
The specific technical scheme is as follows:
the method for improving the performance of the perovskite solar cell through secondary growth of perovskite crystal grains comprises the following specific operations:
1) Sequentially cleaning the transparent conductive substrate by using deionized water, acetone, ethanol and isopropanol, drying the cleaned substrate, treating by using plasma equipment, and standing at normal temperature for standby;
2) Spin-coating a layer of film on the surface of the substrate, wherein the film is PTAA and PEDOT: PSS, niOX, tiO 2 、SnO 2 、ZnO 2 、C 60 、C 70 、PC 61 One or more composite films in the BM;
3) Weighing PbI 2 、PbBr 2 CsI, csBr, FAI preparing a perovskite precursor solution, wherein the perovskite precursor solution is FA 0.8 Cs 0.2 PbI 2.85 Br 0.15 Depositing perovskite precursor solution on the surface of the film in the step 2) in one or more modes of spin coating, knife coating, ink-jet printing and slit coating, and annealing to obtain a Perovskite (PVK) film;
4) Taking a proper amount of Ethyl Thioglycolate (ET), using isopropyl alcohol (IPA) as a solvent to prepare an ethyl thioglycolate/isopropyl alcohol solution, heating and stirring, cooling to room temperature, depositing the ethyl thioglycolate/isopropyl alcohol solution on the surface of the perovskite film obtained in the step 2) in a spin coating mode, and annealing to obtain the perovskite film treated by the ethyl thioglycolate/isopropyl alcohol;
5) Depositing a charge transport layer and a hole blocking layer on the treated perovskite thin film obtained in the step 3);
6) And 5) depositing a metal electrode on the surface of the film obtained in the step 5) to obtain the perovskite solar cell device after the treatment of the ethyl thioglycolate/isopropanol.
Further, the transparent conductive substrate in step 1) is Glass/ITO, glass/FTO, PEN/ITO, PET/ITO, graphene, metal nanowires, carbon nanotubes, conductive polymers, silver, copper or aluminum thin films.
Further, after the perovskite precursor solution in the step 3) is deposited on the surface of the film, annealing is carried out for 10-15 minutes at 100-150 ℃ to obtain the perovskite film.
Further, the concentration of ethyl thioglycolate in the ethyl thioglycolate/isopropanol solution in step 4) was 3.0. 3.0 mg/ml.
Further, the annealing in step 4) is performed at a temperature of 100-150 ℃ for 5-10 minutes, and secondary annealing (under the premise of functional molecule treatment) is helpful for perovskite grain growth.
Further, the charge transport layer in step 5) is PTAA, niOX, tiO 2 、SnO 2 、ZnO 2 、C 60 、C 70 、PC 61 One or more composite films in the BM.
Further, the metal electrode in the step 6) is a composite electrode of one or more of Ag, au and Cu.
The invention has the beneficial effects that:
by introducing ET molecules on the surface of the perovskite, a perovskite film with large grain size, high quality and few grain boundaries (namely few defect sites) is obtained by using a secondary annealing mode; meanwhile, due to the action of sulfhydryl and carbonyl in ET molecules, the ET can effectively passivate defect points, namely uncomplexed lead ions, on the surface of the perovskite film, so that the effect of secondary passivation is achieved, the purpose of improving the film performance is further achieved, and the perovskite solar cell performance is optimized.
Drawings
FIG. 1 is an SEM image of a perovskite thin film before and after ET/IPA treatment.
FIG. 2 is a graph of perovskite thin film grain size statistics before and after ET/IPA treatment.
FIG. 3 is an XRD pattern of perovskite thin films before and after ET/IPA treatment.
FIG. 4 is an ultraviolet absorbance graph of perovskite thin films before and after ET/IPA treatment.
FIG. 5 is a PL plot of the perovskite thin film before and after ET/IPA treatment.
FIG. 6 is a SCLC plot of perovskite thin films before and after ET/IPA treatment.
FIG. 7 is an XPS plot of perovskite thin films before and after ET/IPA treatment.
Fig. 8 is a DFT calculation graph of the adsorption energy of the ET molecules and lead ions on the surface of the perovskite thin film.
Fig. 9 is a Raman plot of ET, pbI2 and ET-PbI 2.
FIG. 10 is a JV graph of perovskite solar cell before and after ET/IPA treatment.
Fig. 11 is a graph showing the trend of the stability change of perovskite solar cell before and after ET/IPA treatment.
Detailed Description
The invention will be further described with reference to the drawings and examples of the specification, but the scope of the invention is not limited thereto.
Example 1
Preparation of Glass/ITO/PTAA/PVK/C60/BCP/Ag perovskite solar cell.
S1, sequentially using deionized water, acetone, ethanol and isopropanol to ultrasonically clean a Glass/ITO substrate, drying, treating by using plasma equipment, and taking out for later use.
S2, spin-coating PTAA solution (2.0 mg/ml, 1ml toluene) on the Glass/ITO surface (6000 rpm, 30 seconds), annealing (100 ℃ for 10 minutes), and standing to normal temperature to obtain the PTAA film.
S3, weighing PbI 2 (426.4 mg), CsI (52 mg), PbBr 2 (27.5 mg), FAI (137.6 mg), using 1ml of the mixed solution (DMF: DMSO, v=3:1) as a solvent, stirring and heating at 60℃for 2 hours, and filtering with a polytetrafluoroethylene filter head having a diameter of 0.22um after allowing to stand at room temperature, to give a clear yellow perovskite precursor solution FA 0.8 Cs 0.2 PbI 2.85 Br 0.15 . Subsequently, 70ul of perovskite precursor solution was spin-coated on the surface of the PTAA film, and annealed at 100 ℃ for 10 minutes to obtain a perovskite film.
S4, taking 3mg of ET, using 1ml of IPA as a solvent to prepare an ET/IPA solution with the concentration of 3mg/ml, heating and stirring at 60 ℃ for 10 minutes, and then cooling to room temperature. And then, depositing the ET/IPA solution on the surface of the PVK film obtained in the step S3 by a spin coating mode, and obtaining the PVK film after the ET/IPA treatment by a secondary annealing mode (100 ℃ for 5 minutes).
S5, sequentially thermally evaporating and depositing an electron transport layer C60 and a hole blocking layer BCP (2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline) with thicknesses of 150 nm and 5 nm respectively, wherein the deposition rates are 0.01nm/s (vacuum degree is less than 1×10) -4 bar), and finally depositing copper metal electrodes.
Taking the perovskite film prepared in the step S3 as a material before ET/IPA treatment and taking the perovskite film prepared in the step S4 as a material after treatment
From FIGS. 1 and 2, it can be seen that the perovskite thin film after ET/IPA treatment has significantly increased grain size and significantly reduced grain boundaries, such that defects at the grain boundariesThe dip is relatively lowered. As shown in FIG. 3, the ET/IPA treated perovskite film has stronger diffraction peak, which shows that the film quality is obviously improved compared with that of untreated perovskite film; in addition, as shown in FIG. 4, the ultraviolet absorption intensity of the perovskite film after ET/IPA treatment is slightly enhanced, and the effect of improving the quality of the perovskite film after ET/IPA treatment is again proved. As shown in the PL test result, the perovskite thin film after ET/IPA treatment has lower fluorescence intensity, which shows that the non-radiative recombination phenomenon of the perovskite thin film after ET/IPA treatment is obviously reduced, and the perovskite thin film is beneficial to the efficient transmission of carriers. Following characterization by SCLC, it was found (FIG. 6) that the ET/IPA treated perovskite had a lower V TFL This indicates that the treated perovskite film has a smaller defect state density, again validating the effect of reducing non-radiative recombination events after ET/IPA treatment. From fig. 1 we know that grain boundary reduction may be one of the reasons for non-radiative recombination decay, and to verify passivation of thiol and carbonyl groups in ET molecules (i.e. that can bind to non-coordinated lead ions present on the perovskite surface), this is demonstrated by relevant tests. As shown in fig. 7, from the XPS test results, the XPS signal position of the lead ions on the surface of the perovskite thin film after the ET/IPA treatment was changed, and it was confirmed that the ET molecules could be combined with the lead ions not coordinated on the surface of the perovskite. The theoretical calculation of DFT shows that (as shown in FIG. 8), the adsorption energy of the mercapto group, carbonyl group and lead ion in the ET molecule is-0.3 eV and-0.28 eV respectively, (the adsorption energy is shown as negative value, which represents the sulfur atom in the mercapto group and the oxygen atom in the carbonyl group can be combined with the lead ion on the surface of perovskite), which indicates that both the mercapto group and the carbonyl group in the ET molecule can be combined with the lead ion, and the adsorption energy of the mercapto group and the lead ion are lower, which indicates that the mercapto group is easier to be combined with the lead ion than the carbonyl group. In order to further verify that both the mercapto group and the carbonyl group in the ET molecule can be combined with lead ions, the ET and the PbI2 are mixed to obtain an ET-PbI2 complex, and Raman tests show that compared with signals of the ET and the PbI2, signals of the mercapto group and the carbonyl group are offset compared with signals of the ET and the PbI2, as shown in FIG. 9, the mercapto group and the carbonyl group in the ET molecule can be effectively combined with the lead ions. As can be seen from the JV test results, as shown in fig. 10,the device processed by the ET/IPA has higher photoelectric conversion efficiency; meanwhile, it was found through stability test (see fig. 11) that the treated device had longer stability. The improvement of photoelectric conversion efficiency and stability can be attributed to the reduction of the surface defect state of the perovskite thin film and the improvement of the grain quality.
Claims (7)
1. The method for improving the performance of the perovskite solar cell through secondary growth of perovskite crystal grains is characterized by comprising the following specific operations:
1) Sequentially cleaning the transparent conductive substrate by using deionized water, acetone, ethanol and isopropanol, drying the cleaned substrate, treating by using plasma equipment, and standing at normal temperature for standby;
2) Spin-coating a layer of film on the surface of the substrate, wherein the film is PTAA and PEDOT: PSS, niOX, tiO 2 、SnO 2 、ZnO 2 、C 60 、C 70 、PC 61 One or more composite films in the BM;
3) Weighing PbI 2 、PbBr 2 CsI, csBr, FAI preparing a perovskite precursor solution, wherein the perovskite precursor solution is FA 0.8 Cs 0.2 PbI 2.85 Br 0.15 Depositing the perovskite precursor solution on the surface of the film in the step 2) in one or more modes of spin coating, knife coating, ink-jet printing and slit coating, and annealing to obtain a perovskite film;
4) Taking a proper amount of ethyl thioglycolate, using isopropanol as a solvent to prepare an ethyl thioglycolate/isopropanol solution, heating and stirring, cooling to room temperature, depositing the ethyl thioglycolate/isopropanol solution on the surface of the perovskite film obtained in the step 2) in a spin coating mode, and obtaining the perovskite film treated by the ethyl thioglycolate/isopropanol in an annealing mode;
5) Depositing a charge transport layer and a hole blocking layer on the treated perovskite thin film obtained by the step 4);
6) And 5) depositing a metal electrode on the surface of the film obtained in the step 5) to obtain the perovskite solar cell device after the treatment of the ethyl thioglycolate/isopropanol.
2. The method of claim 1, wherein the transparent conductive substrate in step 1) is Glass/ITO, glass/FTO, PEN/ITO, PET/ITO, graphene, metal nanowires, carbon nanotubes, conductive polymers, silver, copper, or aluminum thin films.
3. The method according to claim 1, wherein the perovskite precursor solution is deposited on the surface of the film in step 3), and then annealed at 100-150 ℃ for 10-15 minutes to obtain the perovskite film.
4. The process according to claim 1, wherein the concentration of ethyl thioglycolate in the ethyl thioglycolate/isopropyl alcohol solution in step 4) is 1.0-10.0 mg/ml.
5. The method according to claim 1, wherein the annealing in step 4) is performed at a temperature of 100 to 150 ℃ for a time of 5 to 10 minutes.
6. The method of claim 1, wherein the charge transport layer in step 5) is PTAA, niOX, tiO 2 、SnO 2 、ZnO 2 、C 60 、C 70 、PC 61 One or more composite films in the BM.
7. The method of claim 1, wherein the metal electrode in step 6) is a composite electrode of one or more of Ag, au, and Cu.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211652239.8A CN115843189B (en) | 2022-12-22 | 2022-12-22 | Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211652239.8A CN115843189B (en) | 2022-12-22 | 2022-12-22 | Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115843189A CN115843189A (en) | 2023-03-24 |
| CN115843189B true CN115843189B (en) | 2023-07-25 |
Family
ID=85579045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211652239.8A Active CN115843189B (en) | 2022-12-22 | 2022-12-22 | Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115843189B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535969B (en) * | 2023-05-06 | 2024-07-12 | 广汽本田汽车有限公司 | Novel IPA pretreatment solvent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110890466A (en) * | 2019-10-09 | 2020-03-17 | 桂林电子科技大学 | All-printed mesoscopic perovskite solar cell and preparation method thereof |
| WO2021027373A1 (en) * | 2019-08-09 | 2021-02-18 | 杭州纤纳光电科技有限公司 | Crystal seed and method for manufacturing perovskite solar cell thereby |
| CN113097392A (en) * | 2021-03-31 | 2021-07-09 | 合肥工业大学 | Grain boundary passivation method of perovskite solar cell |
| CN113130759A (en) * | 2021-03-05 | 2021-07-16 | 华南理工大学 | Method for rapidly removing surface defects of halide perovskite thin film and application of method in perovskite solar cell |
| KR20210104591A (en) * | 2020-02-17 | 2021-08-25 | 세종대학교산학협력단 | Method for manufacturing perovskite photodiode with improved dark-current property |
| CN113675343A (en) * | 2021-08-17 | 2021-11-19 | 华南农业大学 | Perovskite thin film adopting multifunctional group ligand quantum dots and preparation and application thereof |
-
2022
- 2022-12-22 CN CN202211652239.8A patent/CN115843189B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021027373A1 (en) * | 2019-08-09 | 2021-02-18 | 杭州纤纳光电科技有限公司 | Crystal seed and method for manufacturing perovskite solar cell thereby |
| CN110890466A (en) * | 2019-10-09 | 2020-03-17 | 桂林电子科技大学 | All-printed mesoscopic perovskite solar cell and preparation method thereof |
| KR20210104591A (en) * | 2020-02-17 | 2021-08-25 | 세종대학교산학협력단 | Method for manufacturing perovskite photodiode with improved dark-current property |
| CN113130759A (en) * | 2021-03-05 | 2021-07-16 | 华南理工大学 | Method for rapidly removing surface defects of halide perovskite thin film and application of method in perovskite solar cell |
| CN113097392A (en) * | 2021-03-31 | 2021-07-09 | 合肥工业大学 | Grain boundary passivation method of perovskite solar cell |
| CN113675343A (en) * | 2021-08-17 | 2021-11-19 | 华南农业大学 | Perovskite thin film adopting multifunctional group ligand quantum dots and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115843189A (en) | 2023-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108598268B (en) | Method for preparing planar heterojunction perovskite solar cell by printing under environmental condition | |
| CN109980092B (en) | Perovskite quantum dot solar cell and preparation method thereof | |
| CN108807694B (en) | Flat perovskite solar cell with ultralow temperature stability and preparation method thereof | |
| CN108899420A (en) | The preparation method and perovskite solar cell device of perovskite thin film | |
| CN109888108B (en) | Biomacromolecule modified perovskite solar cell and preparation method thereof | |
| CN115843189B (en) | Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains | |
| CN105870342B (en) | The method of interface processing preparation high-performance perovskite thin film | |
| CN116234331A (en) | Perovskite solar cell based on benzamide bromine modification and preparation method thereof | |
| Onimisi et al. | Size effects of silver nanoparticles on the photovoltaic performance of a dye sensitized solar cells | |
| CN104241411A (en) | Efficient cadmium telluride nanocrystalline Schottky junction solar cell with modified anode interface and preparing method thereof | |
| Wang et al. | Effective control of the length of ZnO-TiO2 nanorod arrays as electron transport layer of perovskite solar cells with enhanced performance | |
| Chen et al. | Enhanced efficiency and stability of perovskite solar cells based on carbon-counter-electrode via anti-solvent treatment | |
| CN109873078B (en) | Perovskite solar cell and preparation method thereof | |
| CN113725368B (en) | NH (NH) 4 NO 3 Perovskite solar cell with modified interface | |
| CN114883503A (en) | Few layer TiO 2 -MXene composite material and preparation method and application thereof | |
| CN113097388B (en) | Perovskite battery based on composite electron transport layer and preparation method thereof | |
| CN109216552B (en) | Bi2O2Preparation method of S-coated nanorod array and application of S-coated nanorod array in solar cell | |
| CN109851571B (en) | Conjugated organic small molecule interface modification material, preparation method and organic solar cell formed by conjugated organic small molecule interface modification material | |
| Wang et al. | Boosting efficiency of planar heterojunction perovskite solar cells by a low temperature TiCl4 treatment | |
| EP4273942A1 (en) | Perovskite solar cell and preparation method therefor | |
| CN113380951B (en) | Perovskite solar cell based on green anti-solvent method and preparation method thereof | |
| CN110098331B (en) | CdTe nano crystal film with surface passivation treatment, surface passivation treatment method and application thereof | |
| Liu et al. | High efficiency stable planar perovskite solar cells via heavy water additive | |
| CN110400875B (en) | Based on TiO2Preparation method of nano-tube perovskite battery electrode | |
| Tung et al. | Effect of Cd1-xMnxSe alloy thickness on the optical and photovoltaic properties of quantum dot-sensitized solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |